The effect of nonsupported MoO3 as a conditioning catalyst on the preparation of carbon nanotubes (CNTs) using a common main catalyst Fe/MgO was investigated. Without using MoO3, only single-walled CNTs were produced at low yield. In contrast, the use of MoO3 provided single-walled and double-walled CNTs at high yield. The MoO3 conditioning catalyst enhances not only the yield but also the diameter and layer number of CNTs. The higher yield formation of more layered CNTs with larger diameter would be attributed to the preproduction of reactive hydrocarbon species by the conditioning catalyst and their growth to larger molecular-weight reactive species.

Mg2Ni1-xCux (x = 0, 0.2, 0.4) and Mg2Ni1-yCoy (y = 0, 0.2, 0.4) were successfully synthesized via two steps: induction melting and then ball milling. The component and microstructure of the alloys were determined with x-ray diffraction (XRD) and scanning electron microscopy/x-ray energy-dispersive spectrometry (SEM/XEDS). Mg2Ni phase was observed in all 5 alloys. When the amount of Cu was increased, it led to the formation of phase from Mg2Cu to Cu11Mg10Ni9. Co2Mg was detected in the Co-containing alloys. The hydrogen absorption/desorption properties were tested with p-C-T measurement apparatus, and the results showed that the gaseous storage properties of the alloys were improved by the addition of Cu or Co.

In the present study, we compared cytotoxicity and cell uptake of silica nanoparticles with four different surface coatings generated through layer-by-layer self-assembly. Rabbit mesenchymal stem cells (rMSCs) were labeled with silica nanoparticles of different coatings including poly(ethyleneimine) (PEI), poly(allylamine hydrochloride) (PAH), poly(anetholesulfonic acid, sodium salt) (PAS), and dextran sulfate. The MTT [3-(4, 5-dimethylthiazol-2)-2, 5-diphenyl-2H-tetrazolium bromide] test was performed to quantify the cell biocompatibility. The cellular uptake of those silica nanoparticles was determined by flow cytometry and confocal laser scanning microscopy. The results showed that all examined silica nanoparticles were stable in aqueous phase with high monodispersity. Labeled rMSCs are unaffected in their viability, apoptosis, and differentiation capacities. The silica nanoparticle-coated synthetic polycations such as PEI or PAH have higher cell internalization than negatively charged polyelectrolytes. The ability to control cell uptake of different particles may have applications in cell labeling, cell separation, and other biomedical applications.

The isometric, pyrochlore structure type, A2B2O7, exhibits a wide variety of properties that find application in a large number of different technologies, from electrolytes in solid oxide fuel cells to actinide-bearing compositions that can be used as nuclear waste forms or inert matrix nuclear fuels. Swift xenon ions (1.43 GeV) have been used to systematically modify different compositions in the Gd2Zr2-xTixO7 binary at the nanoscale by radiation-induced phase transitions that include the crystalline-to-amorphous and order-disorder structural transformations. Synchrotron x-ray diffraction, Raman spectroscopy, and transmission electron microscopy provide a complete and consistent description of structural changes induced by the swift heavy ions and demonstrate that the response of pyrochlore depends strongly on chemical composition. The high and dense electronic energy deposition primarily results in amorphization of Ti-rich pyrochlore; whereas the formation of the fully disordered, defect-fluorite structure is the dominant process for Zr-rich pyrochlore.

A first-principles method was used to investigate the structural and energetic properties for A2Ti2O7 (A = Lu, Er, Y, Gd, Sm, Nd, La), including the formation energies of the cation antisite-pair, the anion Frenkel pair that defines anion-disorder, and the coupled cation antisite-pair/anion-Frenkel. It is proposed that the 〈A–O48f〉 interaction may have more significant influence on the radiation resistance behavior of titanate pyrochlores, although the 〈Ti–O48f〉 interactions are relatively stronger than the 〈A–O48f〉 interactions. It was found that the defect formation energies are not simple functions of the A-site cation radii. The formation energy of the cation antisite-pair increases continuously as the A-site cation varies from Lu to Gd, and then decreases continuously with the variation of the A-site cation from Gd to La, in excellent agreement with the radiation-resistance trend of the titanate pyrochlores. The band gaps in these pyrochlores were also measured, and the band gap widths changed continuously with cation radius.

The residual stress and lattice-parameter depth profiles in a γ′-Fe4N1-x layer (6-μm thickness) grown on top of an α-Fe substrate were investigated using x-ray diffraction stress analysis at constant penetration depths. Three different reflections (220, 311, and 222) were recorded at six different penetration depths using three different wavelengths. At each penetration depth, x-ray diffraction stress analysis was performed on the basis of the sin2ψ method. As a result, the residual-stress depth profile was obtained from the measured lattice strains. The lattice spacings measured in the strain-free direction were used to determine the (strain-free) lattice-parameter depth profile. The nitrogen-concentration depth profile in the layer was calculated by applying a relationship between the (strain-free) γ′ lattice parameter and the nitrogen concentration. It was found that the strain-free lattice-parameter depth profile as derived from the 311 reflections is best compatible with nitrogen concentrations at the surface and at the γ′/α interface as predicted on the basis of local thermodynamic equilibrium. It could be shown that the 311 reflection is most suitable for the analysis of lattice-parameter and residual stress depth profiles because the corresponding x-ray elastic constants exhibit the least sensitivity to the type of and changes in grain interaction. The depth-dependence of the grain interaction could be revealed. It was found that the grain interaction changes from Voigt-type near the surface to Reuss-type at the layer/substrate interface.

A new method for measuring plastic properties of thin films deposited on a substrate is presented. Micrometric cylindrical specimens with the axis perpendicular to the film surface were prepared by milling out the surrounding material using the focused ion beam technique. Such specimens were deformed by means of a nanoindenter outfitted with a flat diamond tip. An equivalent to the macroscopic compressive curve was obtained. Elastic modulus and hardness of the film were then measured using a Berkovich tip. The precise knowledge of the gage length and the independent measurement of elastic properties enable the accurate determination of the stress–strain curve. As compared with the results published in the literature on the specimens with the same dimensions, the studied material deforms less heterogeneously, probably as a consequence of the symmetric crystallographic orientation of the specimens.

Synthetic Cd1–xZnxTe or “CZT” crystals are highly suitable for γ-spectrometers operating at room temperature. Secondary phases (SP) within CZT, presumed to be Te metal, have detrimental impacts on the charge collection efficiency of fabricated device. Using analytical techniques rather than arbitrary theoretical definitions, we identify two SP morphologies: (i) many void, 20-μm “negative” crystals with 65-nm nanoparticle residues of Si, Cd, Zn, and Te and (ii) 20-μm hexagonal-shaped bodies, which are composites of metallic Te layers with cores of amorphous and polycrystalline CZT material that surround the voids.

The enthalpies of oxidative drop solution (ΔHds) for a series of CdSxSe1–x samples were obtained by calorimetry in molten 3Na2O·4MoO3 at 975 K. They become more exothermic linearly with increasing S content. The enthalpies of formation from the elements (ΔHf,el) depend linearly on molar ratio of S/(S + Se). This is the first report of thermodynamic properties of CdSxSe1–x solid solutions measured by any direct calorimetric method. The enthalpies of formation at 298 K from the binary chalcogenide end-members (ΔHf,CdM) (M = S, Se) for wurtzite CdSxSe1–x are found to be zero within experimental errors. These results strongly suggest that wurtzite CdS and CdSe form an ideal solid solution, despite a substantial difference in molar volume and anion radius. This implies that size difference affects thermodynamics less strongly when larger and more polarizable anions are mixed in chalcogenides than when cations are mixed in oxides.

In2Se3, Cu2Se, and CuInSe2 thin films have been successfully fabricated using novel metal organic decomposition (MOD) precursors and atmospheric pressure-based deposition and processing. The phase evolution of the binary (In-Se and Cu-Se) and ternary (Cu-In-Se) MOD precursor films was examined during processing to evaluate the nature of the phase and composition changes. The In-Se binary precursor exhibits two specific phase regimes: (i) a cubic-InxSey phase at processing temperatures between 300 and 400 °C and (ii) the γ-In2Se3 phase for films annealed above 450 °C. Both phases exhibit a composition of 40 at.% indium and 60 at.% selenium. The binary Cu-Se precursor films show more diverse phase behavior, and within a narrow temperature processing range a number of Cu-Se phases, including CuSe2, CuSe, and Cu2Se, can be produced and stabilized. The ternary Cu-In-Se precursor can be used to produce relatively dense CuInSe2 films at temperatures between 300 and 500 °C. Layering the binary precursors together has provided an approach to producing CuInSe2 thin films; however, the morphology of the layered binary structure exhibits a significant degree of porosity. An alternative method of layering was explored where the Cu-Se binary was layered on top of an existing indium-gallium-selenide layer and processed. This method produced highly dense and large-grained (>3 µm) CuInSe2 thin films. This has significant potential as a manufacturable route to CIGS-based solar cells.

Direct conversion of an amorphous carbon (C) film to capsules by gallium (Ga), and nickel and cobalt (NiCo) alloy particles upon heating is investigated in situ by transmission electron microscopy (TEM). Capsules are catalyzed in an NH3 atmosphere when the temperature is raised to 1050 °C. High resolution TEM reveals that graphene flakes initially nucleate at the surface of the catalysts, then segregate and transform into faceted multi-shell capsules upon continued heating. The solubility of carbon in the NiCo alloy particles can be differentiated from the solubility of carbon in Ga particles by the thickness of the walls. The C/Ga binary phase in nanoparticles is discussed regarding the formation of thin-walled carbon capsules.

In literature related to forced hydrolysis of zirconia, heterocoagulation between large particulates and primary crystallites is generally accepted as the principal route of growth. Our dynamic light scattering (DLS) results revealed an S-shaped growth curve with the growth rate (slope) varying notably from one stage to the other, implying that other coagulation mechanisms may be present. Time-sequenced side-by-side electron microscopy and DLS analyses were conducted along the curves alongside with field emission scanning electron microscopy of full-grown particles. We find that particles growth follows a two-stage heterocoagulation process with primary crystallites and small particles produced from the first-stage serving as building blocks for the first and second stages, respectively. It interesting to note that growth during the second stage occurs by self-assembly and a hypothesis is proposed. Convection-induced coagulation leads to enhanced particle growth for a low precursor concentration but minimal growth for a higher one, both of which conform to the predictions of Melis et al. [AIChE J. 45, 1383 (1999)].

Plasticity in amorphous alloys is associated with strain softening, induced by the creation of additional free volume during deformation. In this paper, the role of free volume, which was a priori in the material, on work softening was investigated. For this, an as-cast Zr-based bulk metallic glass (BMG) was systematically annealed below its glass transition temperature, so as to reduce the free volume content. The bonded-interface indentation technique is used to generate extensively deformed and well defined plastic zones. Nanoindentation was utilized to estimate the hardness of the deformed as well as undeformed regions. The results show that the structural relaxation annealing enhances the hardness and that both the subsurface shear band number density and the plastic zone size decrease with annealing time. The serrations in the nanoindentation load-displacement curves become smoother with structural relaxation. Regardless of the annealing condition, the nanohardness of the deformed regions is ∼12–15% lower, implying that the prior free volume only changes the yield stress (or hardness) but not the relative flow stress (or the extent of strain softening). Statistical distributions of the nanohardness obtained from deformed and undeformed regions have no overlap, suggesting that shear band number density has no influence on the plastic characteristics of the deformed region.

The influence of the crystalline orientation of the TiO2 photoanode on the photo-electrochemical characteristics was investigated to reveal the primary factors responsible for improving the photoelectric conversion efficiency of a dye-sensitized solar cell. It was observed that the photocurrent depended on the plane orientation, whereas the dependence of the photopotential on the open circuit was almost constant. The rate of the photoanodic reaction was attributed to the dye adsorption, depending on the surface energy of each oriented plane of the TiO2. The cathodic reaction on TiO2 during open circuit is likely to determine the rate of the entire electrochemical reaction.

Miniaturized test methods were developed and applied to measure the hoop strength of small tubular components. A diametrical loading method and an internal pressurization method using elastomeric insert were adopted in the development of testing methods. Detailed analyses to assess these testing methods were attempted by using theoretical solutions and finite element analysis for stress distributions and the characteristics of the Weibull statistics. To demonstrate the applicability of the test methods, commercially available alumina tubes and miniature silicon carbide coatings from surrogate nuclear fuel particles were tested and their fracture strength distributions were analyzed with Weibull statistics. The size scaling relationship on the fracture strength was investigated by correlating with effective surface area. Furthermore, the applicability of the testing methods was discussed in terms of multiaxial stress fields, altered stress distribution by flattened loading contact, and availability of insert, focusing on high-temperature applications.

A functionalization technique for carbon nanofibers (CNFs) via acid is described. The integrity and chemical nature of the CNFs during the different stages of the applied treatment (oxidation, activation, and functionalization) were examined using different microscopic, chemical, and thermal analysis techniques. The treatment effect on the dispersion ability of the nanofibers in different solvents (tetrahydrofuran, chloroform, and acetone) was also evaluated. Results show that chloroform is the best medium to reach good dispersions and stability of the CNFs in a wide range of concentrations. Using this medium, the functionalization process using 4,4′-diaminodiphenylmethane (DDM) was adopted for the fabrication of reactive CNFs with linker molecules on their surface capable of binding covalently to thermosetting polymers, such as epoxy. The DDM surface derivatized CNFs have been used as reinforcement in epoxy matrix nanocomposites with improved thermomechanical properties in relation to non-treated carbon nanofibers.

New advances toward microstructural improvement of epitaxial CeO2 films grown by chemical solution deposition and their use as buffer layers for YBa2Cu3O7 (YBCO) films are presented. We demonstrate that the degree of epitaxy and the fraction of (001) atomically flat surface area are controlled by the incorporation of tetravalent (Zr4+) or trivalent (Gd3+) cations into the ceria lattice. The degree of epitaxy has been investigated by means of Rutherford backscattering spectroscopy-channeling and reflection high-energy electron diffraction, and a new methodology is also presented to quantify the fraction of (001) atomically flat area from atomic force microscopy images. Results are further correlated with the superconducting properties, microstructure, and texture of YBCO films grown by the trifluoroacetate route. A comparison with pulsed laser deposition and YBCO films grown on the same ceria layers is also presented. This growth procedure has allowed us to obtain all chemical multilayer films with controlled microstructure and critical current densities above 4 MA cm−2 at 77 K.

Indentation tests involving a constant-loading rate stage followed by a constant-load stage were performed on annealed and 20% cold-worked Au to investigate the effect of indentation depth and initial dislocation density on the indentation deformation process. The indentation strain rate data were analyzed in terms of an obstacle-limited dislocation glide mechanism. The apparent activation energy was of the order of 0.16 μb3 and was neither a function of initial indentation depth nor cold work. The results of Haasen plot activation analysis and direct transmission electron microscopy (TEM) observations indicate that more mechanical work must be applied during the constant-loading rate stage due to the large amount of work hardening compared with the constant-load stage where considerably more dislocation recovery occurs.

A rate-change instrumented indentation method is introduced to experimentally characterize the strain rate sensitivity of high strength materials, such as metallic glasses and nanocrystalline metals, which generally possess low rate sensitivity at room temperature. This technique has been validated herein, via self-consistency between rate jump and rate drop measurements, as a viable way to characterize rate dependent deformation behavior and thereby the underlying micromechanisms of plastic flow.

The free corrosion behavior and the anodic passivation ability of the bulk glassy (Fe44.3Cr5Co5Mo12.8Mn11.2C15.8B5.9)98.5Y1.5 alloy were fundamentally analyzed. Electrochemical tests were performed in aqueous solutions with pH values in the interval 0.3–14. Corrosion current densities are below 3 μA/cm2 in the entire studied pH interval; compared with commercial grade steels, for example, X210Cr12 steel, the glassy alloy has lower corrosion rates in acidic electrolytes and higher in basic solutions. The alloy exhibits high dissolution rates upon anodic polarization in acidic environments, but with increasing pH values it tends to form passive layers showing the lowest passive current density at pH 11. The passive layers consist mainly of Fe and Cr oxides. There is a strong variation of the passive layer structure and composition with pH. The protective effect of the grown surface layers is negatively influenced by sulfate ions.